KR102417599B1 - Colored curable resin composition, color filter and display device - Google Patents

Abstract

［식 (I) 중,
R¹ 및 R²는, 각각 독립적으로, 치환기를 가질 수 있는 탄소수 1∼8의 탄화수소기, 할로겐 원자, 또는 －OR³기를 나타내고,
R³은, 치환기를 가질 수 있는 탄소수 1∼8의 탄화수소기를 나타내며,
M^k＋는, k가의 양이온을 나타내고,
k는, 1 이상 5 이하의 정수를 나타내며,
m은, 0 이상 4 이하의 정수를 나타내고, m이 2 이상일 때 복수의 R¹은 동일하거나 상이할 수 있으며,
n은, 1 이상 5 이하의 정수를 나타내고, n이 2 이상일 때 복수의 R²는 동일하거나 상이할 수 있다.］The present invention provides a color filter having excellent contrast and a colored curable resin composition capable of forming a display device. The colored curable resin composition which concerns on this invention contains a coloring agent, resin, a polymeric compound, and a polymerization initiator, It has the characteristics in that the said coloring agent contains the compound represented by Formula (I).

[in formula (I),
R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, a halogen atom, or an —OR ³ group,
R ³ represents a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent,
M ^k+ represents a k-valent cation,
k represents an integer of 1 or more and 5 or less,
m represents an integer of 0 or more and 4 or less, and when m is 2 or more, a plurality of R ¹ may be the same or different,
n represents an integer of 1 or more and 5 or less, and when n is 2 or more, a plurality of R ² may be the same or different.]

Description

Colored curable resin composition, a color filter, and a display device TECHNICAL FIELD

The present invention relates to a colored curable resin composition, a color filter, and a display device.

The color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display, and solid-state imaging elements, such as a CCD and CMOS sensor, is manufactured from a colored curable resin composition. As such a colored curable resin composition, the composition containing C.I. Pigment Red 269 as a coloring agent is known (patent document 1).

(Patent Document 1) Japanese Patent Application Laid-Open No. 2016-170324

However, the color filter formed from said colored curable resin composition known conventionally was not able to fully satisfy|fill contrast. Then, this invention provides the colored curable resin composition which can form the color filter excellent in contrast.

The present invention includes the following inventions.

[1] A colorant, a resin, a polymerizable compound, and a polymerization initiator are included,

Colored curable resin composition in which the said coloring agent contains the compound represented by Formula (I).

(Formula 1)

[in formula (I),

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, a halogen atom, or an —OR ³ group,

R ³ represents a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent,

M ^k+ represents a k-valent cation,

k represents an integer of 1 or more and 5 or less,

m represents an integer of 0 or more and 4 or less, and when m is 2 or more, a plurality of R ¹ may be the same or different,

n represents an integer of 1 or more and 5 or less, and when n is 2 or more, a plurality of R ² may be the same or different.]

[2] A color filter formed from the colored curable resin composition according to [1].

[3] A display device comprising the color filter according to [2].

ADVANTAGE OF THE INVENTION According to this invention, the colored curable resin composition which can form the color filter excellent in contrast is provided.

<Colored curable resin composition>

The colored curable resin composition of this invention contains the compound represented by Formula (I) including a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D).

The colored curable resin composition of this invention can contain a polymerization initiation adjuvant (D1), a solvent (E), and a leveling agent (F) further.

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types, unless otherwise indicated.

<Colorant (A)>

The colored curable resin composition of this invention contains the compound (henceforth "compound (I)") represented by Formula (I) as a coloring agent (A).

(Formula 1)

[in formula (I),

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, a halogen atom, or an —OR ³ group,

R ³ represents a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent,

M ^k+ represents a k-valent cation,

k represents an integer of 1 or more and 5 or less,

m represents an integer of 0 or more and 4 or less, and when m is 2 or more, a plurality of R ¹ may be the same or different,

n represents an integer of 1 or more and 5 or less, and when n is 2 or more, a plurality of R ² may be the same or different.]

The hydrocarbon group having 1 to 8 carbon atoms which may have a substituent represented by R ¹ , R ² , and R ³ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent or 6 to 8 carbon atoms which may have a substituent. of an aromatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms for R ¹ , R ² , and R ³ may be any of linear, branched and cyclic.

Examples of the linear or branched aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; Branched aliphatic hydrocarbon groups, such as a tyl group, a neopentyl group, and 2-ethylhexyl group, etc. are mentioned. Carbon number of the said aliphatic hydrocarbon group becomes like this. Preferably it is 1-6, More preferably, it is 1-5, More preferably, it is 1-4.

The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Carbon number of the said cyclic aliphatic hydrocarbon group becomes like this. Preferably it is 3-8, More preferably, it is 3-6.

Examples of the aromatic hydrocarbon group having 6 to 8 carbon atoms in R ¹ , R ² , and R ³ include a phenyl group, a tolyl group, a xylyl group, a phenethyl group, and an α-methylbenzyl group. Preferably carbon number of the said aromatic hydrocarbon group is six.

The hydrocarbon group having 1 to 8 carbon atoms represented by R ¹ , R ² , and R ³ may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; a nitro group; a cyano group. ; Amino group; Hydroxy group; Methoxy group, alkoxy group having 1 to 6 carbon atoms such as ethoxy group; sulfanyl group; alkylsulfanyl group having 1 to 6 carbon atoms, such as methylsulfanyl group and ethylsulfanyl group; Alkoxycarbonyl groups having 1 to 6 carbon atoms such as oxycarbonyl group and ethoxycarbonyl group; sulfo group; sulfamoyl group; alkoxysulfonyl group having 1 to 6 carbon atoms such as methoxysulfonyl group and ethoxysulfonyl group; have.

R ¹ , R ² , and R ³ each independently represent a methyl group, an ethyl group, a propyl group, a trifluoromethyl group, or a phenyl group, more preferably a methyl group or an ethyl group. Also, R ¹ , R ² , and R ³ may be the same or different.

As a halogen atom represented by R< ¹ > or R< ² >, a fluorine atom, a chlorine atom, an iodine atom, a bromine atom, etc. are mentioned, Preferably it is a chlorine atom.

The -OR ³ group represented by R ¹ or R ² is particularly preferably a methoxy group or an ethoxy group.

M ^k+ is preferably a hydrogen ion, a k-valent metal ion, or a substituted or unsubstituted ammonium ion.

Examples of the k-valent metal ion represented by M ^k+ include alkali metal ions such as lithium ions, sodium ions and potassium ions; alkaline earth metal ions such as magnesium ions, calcium ions, strontium ions, and barium ions; titanium ions, zirconium ions, chromium ions, Transition metal ions such as manganese ions, iron ions, cobalt ions, nickel ions, and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and bismuth ions; have.

Examples of the substituted or unsubstituted ammonium ion represented by M ^k+ include quaternary ammonium ions such as tetraalkylammonium ions.

M ^k+ is preferably a hydrogen ion or a k-valent metal ion, more preferably a hydrogen ion, an alkali metal ion, or an alkaline earth metal ion, still more preferably an alkaline earth metal ion. As M ^k+ , a hydrogen ion, a sodium ion, a potassium ion, a magnesium ion, a strontium ion, a barium ion, a zirconium ion, a manganese ion, or a zinc ion is preferable, and a hydrogen ion or a barium ion is even more preferable.

k becomes like this. Preferably it is 4 or less, More preferably, it is 3 or less, More preferably, it is 1 or 2.

m becomes like this. Preferably it is 3 or less, More preferably, it is 2 or less, More preferably, it is 1 or less, Even more preferably, it is 0. When m is 2 or more, a plurality of R ¹ may be the same or different.

n becomes like this. Preferably it is 2 or more, Preferably it is 5 or less, More preferably, it is 4 or less, More preferably, it is 3 or less, Especially preferably, it is 3. When n is 2 or more, a plurality of R ² may be the same or different.

The compound (I) preferably has a valence of 0, that is, an electrically neutral compound.

The compound (I) is preferably a compound represented by formula (II) (hereinafter sometimes referred to as “compound (II)”).

(Formula 2)

[in formula (II),

R ²¹ to R ²⁵ are each independently a hydrogen atom, a halogen atom or a -OR ³ group, at least one of R ²¹ to R ²⁵ is a halogen atom or a -OR ³ group,

R ¹ , m, R ³ , M ^k+ and k are the same as above.]

As a halogen atom in Formula (II), a fluorine atom, a chlorine atom, an iodine atom, a bromine atom, etc. are mentioned, Preferably it is a chlorine atom.

Among R ²¹ to R ²⁵ , preferably 2 or more (preferably 4 or less) are halogen atoms and/or -OR ³ groups, more preferably 3 of R ²¹ to R ²⁵ are halogen atoms and/or or -OR ³ group.

In formula (II), either one of R ²¹ or R ²³ or both R ²¹ and R ²³ , more preferably R ²¹ and R ²³ are —OR ³ groups.

Further, in formula (II), either one of R ²⁴ or R ²⁵ or both R ²⁴ and R ²⁵ , more preferably R ²⁴ is a halogen atom.

As the compound (II), at least one or more selected from the compound represented by the formula (II-a), the compound represented by the formula (II-b), and the compound represented by the formula (II-c) is preferable. Especially, since the contrast is favorable, the compound represented by Formula (II-b) or the compound represented by Formula (II-c) is preferable, More preferably, it is a compound represented by Formula (II-b).

(Formula 2-1)

(Formula 2-2)

(Formula 2-3)

[In formulas (II-a), (II-b), and (II-c), R ²¹ to R ²⁵ , M ^k+ and k are the same as above.]

As compound (I), the compound etc. which are shown to Tables 1-3 and are represented by Formula (I-1) - Formula (I-216) are mentioned.

Compound (I) is

Preferably, the compound represented by Formula (I-13) - Formula (I-20), the compound represented by Formula (I-85) - Formula (I-92), Formula (I-157) - Formula (I-164) is a compound represented by

More preferably, the compound represented by Formulas (I-13) - Formula (I-16), the compound represented by Formula (I-85) - Formula (I-88), Formula (I-157) - Formula (I-160) ), more preferably a compound represented by a formula (I-85) to a formula (I-88), or a compound represented by a formula (I-157) to a formula (I-160).

In Tables 1 to 3, OMe represents a methoxy group and OEt represents an ethoxy group.

In addition, in Tables 1-3, "PH" represents the phenyl group which SO ₃ ^- and (R ¹ ) _m couple|bond in Formula (I) (* represents a bond with a nitrogen atom), specifically, It means group represented by a formula (Ph1) - a formula (Ph3).

(Formula 3)

The compound represented by the formula (I) (provided that M ^k+ =H ⁺ ) is produced after the compound represented by the formula (pt1) is reacted with a nitrite (for example, sodium nitrite) in an acidic aqueous solution to produce a diazonium salt It can manufacture by making the diazonium salt and the compound represented by Formula (pt2) react. In this reaction, it is preferable that the usage-amount of the compound represented by Formula (pt1) is 0.5-1.5 mol with respect to 1 mol of compounds represented by Formula (pt2).

Further, the compound represented by the formula (I) (provided that M ^k+ ≠H ⁺ ) is the compound represented by the formula (I) (provided that M ^k+ =H ⁺ ) and the k-valent cation M ^k+ (provided that M ^k+ ≠H ^{+ )} ) containing halide (preferably chloride), acetate, phosphate, sulfate, silicate or cyanide, and the like.

(Formula 4)

[In formulas (pt1), (pt2), and (I), R ¹ , R ² , m, n, M ^k+ and k are the same as above.]

The content of the compound (I) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, even more preferably 50% by mass or more, in the total amount of the colorant (A), , 80% by mass or more is particularly preferable, and most preferably 90% by mass or more.

The colored curable resin composition of this invention can contain a dye (A1) and a pigment (A2) other than compound (I) as a coloring agent (A).

A dye (A1) is not specifically limited, A well-known dye can be used, For example, a solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned. As the dye, for example, a compound classified as having a color other than a pigment in the color index (published by The Society of Dyers and Colorists), and a known dye described in a dyeing note (dyed yarn) can be mentioned. In addition, according to the chemical structure, azo dye (however, compound (I) is excluded), cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye , an azomethine dye, a scrylium dye, an acridine dye, a styryl dye, a coumarin dye, a quinoline dye, a nitro dye, etc. are mentioned. Among these, organic solvent-soluble dyes are preferable.

It does not specifically limit as a pigment (A2), A well-known pigment can be used, For example, the pigment classified into the pigment by the color index (The Society of Dyers and Colorists publication) is mentioned.

As a pigment, For example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments;

C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ;

C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60; C.I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments, such as Pigment Green 7, 36, 58;

C.I. Brown pigments, such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

To [ the content rate of a coloring agent (A) ] with respect to the total amount of solid content, Preferably it is 0.1-70 mass %, More preferably, it is 0.5-60 mass %, More preferably, it is 1-50 mass %.

Here, the "total amount of solid content" in this specification means the quantity remove|excluding content of the solvent from the total amount of colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is an alkali-soluble resin, At least 1 type (a) (hereinafter referred to as "(a)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride A resin having a structural unit derived from ) is more preferable. The resin (B) further comprises a structural unit derived from a monomer (b) (hereinafter sometimes referred to as “(b)”) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, (a) and A structural unit derived from a copolymerizable monomer (c) (however, different from (a) and (b)) (hereinafter sometimes referred to as “(c)”), and a structure having an ethylenically unsaturated bond in a side chain It is preferable to have at least one kind of structural unit selected from the group consisting of units.

Specifically as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-(meth)acryloyl oxyethyl], etc. are mentioned, Preferably, they are acrylic acid, methacrylic acid, and maleic anhydride.

(b) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and a (meth)acryloyloxy group is preferable

In addition, in this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations, such as "(meth)acryloyl" and "(meth)acrylate", also have the same meaning.

As (b), for example, glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, 3-ethyl -3-(meth)acryloyloxymethyloxetane, tetrahydrofurfuryl (meth)acrylate, etc. are mentioned, Preferably, glycidyl (meth)acrylate, 3,4-epoxy tricyclo [ 5.2.1.0 ^2,6 ] It is decyl (meth)acrylate and 3-ethyl-3- (meth)acryloyloxymethyloxetane.

As (c), for example, methyl (meth) acrylate, butyl (meth) acrylate cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ]Decan-8-yl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene , vinyltoluene, etc. are mentioned, Preferably, styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, etc. are preferable. do.

The resin having a structural unit having an ethylenically unsaturated bond in the side chain is obtained by adding (b) to the copolymer of (a) and (c), or adding (a) to the copolymer of (b) and (c). It can be manufactured by The resin may be a resin in which (a) is added to the copolymer of (b) and (c) and further reacted with carboxylic acid anhydride.

The polystyrene conversion weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000.

The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) becomes like this in conversion of solid content, Preferably it is 20-170 mg-KOH/g, More preferably, it is 30-150 mg-KOH/g, More preferably, it is 40-135 mg-KOH/g. Here, an acid value is a value measured as quantity (mg) of potassium hydroxide required in order to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

To [ the content rate of resin (B) ] with respect to the total amount of solid content, Preferably it is 7-65 mass %, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, etc., preferably Preferably, it is a (meth)acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , dipentaerythritol hexa(meth)acrylate, and the like.

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, they are 250 or more and 1,500 or less.

It is preferable that content rate of a polymeric compound (C) is 7-65 mass % with respect to the total amount of solid content, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical, an acid, etc. under the action of light or heat, and a known polymerization initiator can be used. As a polymerization initiator which generate|occur|produces an active radical, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulf), for example. Panylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, 2-methyl-2-morph Polyno-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexyl Phenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis( 2-chlorophenyl) -4, 4', 5, 5'-tetraphenylbiimidazole, etc. are mentioned.

To [ content of a polymerization initiator (D) / 100 mass parts of total amounts of resin (B) and a polymeric compound (C)), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

The colored curable resin composition of this invention can contain the polymerization initiation adjuvant (D1).

<Polymerization initiation aid (D1)>

The polymerization initiation adjuvant (D1) is a compound or sensitizer used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator. When a polymerization initiation adjuvant (D1) is included, it is used in combination with a polymerization initiator (D) normally.

Examples of the polymerization initiation auxiliary (D1) include 4,4'-bis(dimethylamino)benzophenone (common name mihirazketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc. are mentioned.

When using these polymerization initiation adjuvant (D1), the content is with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. is the mass part. When the amount of the polymerization initiation adjuvant (D1) is within this range, a coloring pattern can be formed more highly sensitively, and the productivity of the color filter tends to be improved.

The colored curable resin composition of this invention can contain the solvent (E).

<Solvent (E)>

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule, - solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

As a solvent,

Ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and γ-butylolactone (in the molecule - Solvent containing COO- and not containing -O-);

Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (in the molecule -O- A solvent that contains and does not contain -COO-);

Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate (in the molecule Solvent containing -COO- and -O-);

Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, and cyclohexanone (with -CO- in the molecule and not -COO- solvent);

Alcohol solvents, such as butanol, cyclohexanol, and propylene glycol (a solvent which contains OH in a molecule|numerator and does not contain -O-, -CO-, and -COO-);

Amide solvents, such as N,N- dimethylformamide, N,N- dimethylacetamide, and N-methylpyrrolidone; etc. are mentioned.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone are more preferable.

When a solvent (E) is included, with respect to the total amount of the colored curable resin composition of this invention, the content rate of a solvent (E) becomes like this. Preferably it is 70-95 mass %, More preferably, it is 75-92 mass %. In other words, the total amount of solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When content of a solvent (E) exists in said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

The colored curable resin composition of this invention can contain a leveling agent (F).

<Leveling agent (F)>

As a leveling agent (F), the silicone type surfactant etc. which have a silicone type surfactant, a fluorine type surfactant, and a fluorine atom are mentioned. These may have a polymerizable group in a side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: Toray Dow Corning Co., Ltd. make), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company). .

As said fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, dong FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, dong F171, dong F172, dong F173, dong F177, dong F183, dong F554, dong R30, RS-718-K (manufactured by DIC Co., Ltd.), FTOP (registered trademark) EF301, EF303, copper EF351, EF352 (manufactured by Misbishi Material Electronics Chemical Co., Ltd.), Surflon (registered trademark) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Refining Chemical Research Institute), and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapack (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

To [ content of a leveling agent (F) ] when including a leveling agent (F) with respect to the total amount of colored curable resin composition, Preferably it is 0.001-0.2 mass %, More preferably, it is 0.002-0.1 mass %. In addition, content of a pigment dispersant is not contained in this content. When content of a leveling agent (F) exists in said range, the flatness of a color filter can be made favorable.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other high molecular compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like, if necessary.

<Method for producing colored curable resin composition>

The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a polymerization initiation auxiliary (D1), a solvent (E), It can prepare by mixing a leveling agent (F) and another component.

<The manufacturing method of a color filter>

As a method of manufacturing a colored pattern from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable.

When colored curable resin composition contains compound (I) as a coloring agent, especially the color filter excellent in contrast can be produced. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

<Example>

Hereinafter, the colored curable resin composition of this invention is demonstrated in more detail by an Example. In the examples, “%” and “parts” are mass% and parts by mass, unless otherwise specified.

[Synthesis Example 1]

After adding 100 parts of water to 17.3 parts of orthanylic acid, 4.0 parts of sodium hydroxide was added and it was made to melt|dissolve. Under ice cooling, 21.7 parts of 35% aqueous sodium nitrite solution was added, and then, 11.5 parts of 35% hydrochloric acid were added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

37.6 parts of 5'-chloro-3-hydroxy-2',4'-dimethoxy-2-naphthoanilide was suspended in 100 parts of water, and pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the said diazonium salt was dripped here over 15 minutes. After completion of the dropwise addition, a yellow suspension was obtained by further stirring for 30 minutes. After stirring the suspension for 1 hour, the mixture was further stirred for 1 hour. The red solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 53.2 parts of compounds represented by Formula (I-1) were obtained.

5.4 parts of the compound represented by Formula (I-1) was added to 100 parts of water, and the liquid (aqueous solution 1) in which the compound represented by Formula (I-1) was dissolved was prepared. Separately, a liquid (aqueous solution 2) in which 4.9 parts of barium chloride dihydrate was dissolved in 80 parts of water was prepared, and the aqueous solution 2 was added dropwise to the aqueous solution 1 at 40°C over 2 hours. After that, it stirred for 4 hours. After cooling, it filtered, washed twice with 100 parts of ion-exchange water, and the crystal|crystallization was dried under reduced pressure at 100 degreeC, and 6.8 parts of compounds represented by Formula (I-13) were obtained.

(Formula 5-1)

[Synthesis Example 2]

In Synthesis Example 1, except that methanilic acid was used instead of orthanylic acid, it was carried out in the same manner as in Synthesis Example 1 to obtain compounds represented by formulas (I-73) and (I-85), respectively.

(Formula 5-2)

[Synthesis Example 3]

In Synthesis Example 1, except that sulfanilic acid was used instead of orthanylic acid, in the same manner as in Synthesis Example 1, compounds represented by formulas (I-145) and (I-157) were obtained, respectively.

(Formula 5-3)

[Resin Synthesis Example 1]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed into a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was put, and the mixture was heated to 80°C while stirring. Next, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane- The solution which melt|dissolved 289 parts of the mixture (content ratio 1:1) of 9-yl acrylate in 125 parts of propylene glycol monomethyl ether acetate was dripped over about 5 hours using the dropping pump. On the other hand, a solution obtained by dissolving 33 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over about 6 hours using another dropping pump. After completion|finish of dripping, it preserve|maintained at the same temperature for 4 hours, it cooled to room temperature, and obtained the copolymer (resin (B-1)) solution of 35.1% of solid content. The weight average molecular weight Mw of the produced|generated copolymer was 9200, the dispersion degree was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. Resin (B-1) has the following structural unit.

(Formula 6)

[Resin Synthesis Example 2]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed into the flask, replaced with a nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was put, and the mixture was heated to 85°C while stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic A mixed solution of 225 parts of the mixture (content is 1:1), 81 parts of vinyl toluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, the solution which melt|dissolved 30 parts of polymerization initiator 2,2- azobis (2, 4- dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was dripped over 5 hours. After completion of the dropwise addition of the initiator solution, the solution was kept at the same temperature for 4 hours, cooled to room temperature, and a copolymer (resin (B-2)) solution having a B-type viscosity (23°C) of 246 mPa·s and a solid content of 37.5% was obtained. . The weight average molecular weight Mw of the produced|generated copolymer was 10600, the dispersion degree 2.01, and the acid value in conversion of solid content was 112 mg-KOH/g. Resin (B-2) has the following structural unit.

(Formula 7)

The measurement of the polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) of resin was performed on condition of the following by gel permeation chromatography (GPC method).

Apparatus 　　　　　; HLC-8120 GPC (manufactured by Toso Co., Ltd.)

Column　　　　　；TSK-GELG2000HXL

Column temperature 　　; 40℃

Solvent　　　　　；THF

Flow rate　　　　　; 1.0mL/min

Test solution solid content concentration; 0.001 to 0.01 mass %

Injection volume　　　　; 50μL

Detector　　　　；RI

Calibration standard;TSK　STANDARD　POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(manufactured by Toso Co., Ltd.)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into the dispersion degree.

(Preparation of colored curable resin composition)

[Preparation of dispersion (P-1)]

10 parts of the compound represented by Formula (I-13), 13.3 parts of a dispersing agent (BYK-LPN21116 made by BYK; 60% propylene glycol monomethyl ether acetate solution), 8 parts of resin (B-2) (solid content conversion) 8 parts, 4-hyde 20 parts of roxy-4-methyl-2-pentanone and 149 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.2 micrometers zirconia beads were added, and it shook for 6 hours using the paint conditioner (made by LAU). Then, the zirconia beads were removed by filtration, and the dispersion liquid (P-1) was obtained.

[Preparation of dispersion (P-2)]

10 parts of the compound represented by formula (I-85), 16.7 parts of a dispersing agent (BYK-LP N21116; 60% propylene glycol monomethyl ether acetate solution by BYK company), 8 parts of resin (B-2) (solid content conversion) 8 parts, 4- 20 parts of hydroxy-4-methyl-2-pentanone and 145 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.2 micrometers zirconia beads were added, and it shook for 3 hours using the paint conditioner (made by LAU). Then, the zirconia beads were removed by filtration, and the dispersion liquid (P-2) was obtained.

[Preparation of dispersion (P-3)]

A dispersion (P-3) was prepared in the same manner as in the preparation of the dispersion (P-2) except that the compound represented by the formula (I-85) was replaced with the compound represented by the formula (I-157).

[Preparation of dispersion (P-4)]

A dispersion (P-4) was produced in the same manner as in the preparation of the dispersion (P-2) except that the compound represented by the formula (I-85) was replaced with C.I. Pigment Red 269.

Each component was mixed so that it might become a composition shown in Table 4, and the colored curable resin composition was obtained.

In Table 4, each component shows the following compounds.

(B-1): Resin (B-1) (in terms of solid content)

(C-1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF)

(E-1): Propylene glycol monomethyl ether acetate

(E-2): 4-hydroxy-4-methyl-2-pentanone

(F-1): Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.)

<Production of color filter>

After apply|coating a colored curable resin composition by the spin coating method on the glass substrate (Eagle 2000; Corning company make) of 5 cm corner, it prebaked at 100 degreeC for 3 minutes, and the coloring composition layer was obtained. After standing to cool, in oven, post-baking was performed at 230 degreeC for 20 minutes, and the color filter was obtained.

<Contrast evaluation>

About the obtained color filter, a blank was used using the contrast meter (CT-1; Tsubosaka Electric Co., Ltd. make, color difference meter BM-5A; Topcon Corp. make, light source; F-10, Polarizing film; Tsubosaka Electric Co., Ltd. make) Contrast was measured with a value of 30000. A result is shown in Table 5.

According to the colored curable resin composition of this invention, the color filter excellent in contrast can be produced.

Claims (3)

a colorant, a resin, a polymerizable compound, and a polymerization initiator;
Colored curable resin composition in which the said coloring agent contains the compound represented by Formula (I).
(Formula 1)

[in formula (I),
R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, a halogen atom, or an —OR ³ group,
R ² contains at least one halogen atom,
R ³ represents a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent,
M ^k+ represents a k-valent cation,
k represents an integer of 1 or more and 5 or less,
m represents an integer of 0 or more and 4 or less, and when m is 2 or more, a plurality of R ¹ may be the same or different,
n represents an integer of 1 or more and 5 or less, and when n is 2 or more, a plurality of R ² may be the same or different.] The color filter formed from the colored curable resin composition of Claim 1. A display device comprising the color filter of claim 2 .